EP0952147B1 - Procédé de sulfochloration photochimique d'alcanes gazeux - Google Patents

Procédé de sulfochloration photochimique d'alcanes gazeux Download PDF

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Publication number
EP0952147B1
EP0952147B1 EP99400724A EP99400724A EP0952147B1 EP 0952147 B1 EP0952147 B1 EP 0952147B1 EP 99400724 A EP99400724 A EP 99400724A EP 99400724 A EP99400724 A EP 99400724A EP 0952147 B1 EP0952147 B1 EP 0952147B1
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EP
European Patent Office
Prior art keywords
mol
chlorine
alkane
process according
reactor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99400724A
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German (de)
English (en)
French (fr)
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EP0952147A1 (fr
Inventor
Jean Ollivier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
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Atofina SA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/123—Ultraviolet light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
    • C07C303/10—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfur dioxide and halogen or by reaction with sulfuryl halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00105—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling
    • B01J2219/0011—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling involving reactant liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00121—Controlling the temperature by direct heating or cooling
    • B01J2219/00123—Controlling the temperature by direct heating or cooling adding a temperature modifying medium to the reactants

Definitions

  • the present invention relates to the field of alkanesulfonyl chlorides and more particularly relates to the manufacture of these compounds by sulfochlorination photochemical of gaseous alkanes at room temperature.
  • alkanesulfonyl chlorides in particular methanesulfonyl chloride
  • the production of these compounds was the subject of several processes consisting in particular of photochemical sulfochlorination alkanes with chlorine and sulfur dioxide.
  • photochemical sulfochlorination alkanes with chlorine and sulfur dioxide is the one described in FR 2,578,841 and FR 2,595,095.
  • This process which essentially consists in reacting a gaseous mixture alkane, sulfur dioxide and chlorine in the presence of ultraviolet light provided by a mercury lamp, is characterized in that the mixture contains a large excess of sulfur dioxide over the alkane and only sulfur dioxide liquid is injected into the reaction zone to keep the temperature constant of it.
  • An installation for implementing this process is also described in the aforementioned patents, the content of which is incorporated herein by reference.
  • the subject of the invention is therefore a process for the manufacture of alkanesulfonyl chlorides by photochemical reaction of an alkane with chlorine and dioxide sulfur, possibly in the presence of hydrogen chloride, characterized in that a medium pressure mercury lamp is used as the light source gallium doped.
  • the process according to the invention relates more particularly to the sulfochlorination of methane which is the most difficult alkane to sulfochlorinate, but it also applies to all gaseous alkanes under the chosen temperature and pressure conditions.
  • the proportions of reactants in the gas mixture subjected to light radiation can vary between the following limits: per mole of methane per mole of C 2 alkane or more SO 2 1 to 12 moles 7 to 14 moles Cl 2 0.1 to 1 mole 0.1 to 1 mole HCI 0.1 to 0.6 mole 0 and are preferably chosen as follows: SO 2 5 to 7 moles 10 to 13 moles Cl 2 0.7 to 0.9 mole 0.7 to 0.9 mole HCI 0.4 to 0.5 mole 0
  • this pressure can range from 1 to 15 bars relative and is, from preferably between 8 and 12 relative bars.
  • the reaction temperature generally between 10 and 90 ° C, depends on the working pressure chosen. It is for example around 60 ° C for 10 bar absolute and around 80 ° C for 15 bar absolute. As in the process described in patents FR 2 578 841 and FR 2 595 095, the temperature is kept constant by injection of liquid SO 2 into the reaction zone.
  • Gallium-doped medium pressure mercury lamps to be used according to the process according to the invention are well known and are described, for example, in chapter 9 of R.Philips' book “Sources and Applications of Ultraviolet Radiation "Academic Press 1983, p.264-276 whose content is incorporated here by reference.
  • Such lamps marketed by the HERAEUS Companies, SILITRO / SCAM and PHILIPS, re-emit more than 60% of their light energy in the form of radiation of wavelengths between 400 and 485 nm.
  • the Figures 1 and 2 attached show respectively the emission spectrum of a lamp 750 watt medium pressure mercury and that of a mercury lamp medium pressure of the same power doped with gallium.
  • the method according to the invention can be implemented in an installation similar to that described in patent FR 2 578 841.
  • Such an installation comprising essentially means for supplying reagents, a photochemical reactor and means for separating the reaction products is represented by the schematic drawing of Figure 3 attached.
  • the inputs 1, 2 and 3 are respectively those of the alkane, sulfur dioxide and chlorine which are introduced in the gaseous state into a mixer 4 provided with an agitator to homogenize the gas mixture. ; for safety reasons, a premixer of Cl 2 and SO 2 is preferably provided at 4 '.
  • the gas mixture passes from the mixer 4 via the line 5 into the reactor 6 in which it is distributed uniformly by means of a ramp 5 'with orifices.
  • Another similar ramp 7 is also placed along the height of the reactor to introduce the liquid SO 2 intended for adjusting the temperature.
  • a light source 8 passes through the reactor in a manner known per se.
  • a tube 11 leads the liquid product, formed in the reactor 6, to a separator 12 from which the liquid phase, that is to say the crude alkanesulfonyl chloride, descends into an intermediate storage 13 , while the residual gases pass through a line 14 in a second separator 15.
  • This separator is optionally provided with a cooler 15 'to bring the SO 2 , arriving, to the liquid state; the liquid SO 2 containing chlorine is recovered in an intermediate storage 16.
  • a fraction of SO 2 is recycled by the pipes 17 and 17 ′ via the pump 18 and the ramp 7 in the reactor 6.
  • Another fraction of SO 2 , coming from 16, goes through line 19 in the heater 20 and from there through 19 'to the supply of the mixer 4.
  • the HCI is evacuated via line 21 to processing devices not shown.
  • a line 22 to apparatuses for purifying alkanesulfonyl chloride product which, not being the subject of the invention, is not shown here.
  • methanesulfonyl chloride (CH 3 SO 2 Cl) was prepared using a medium pressure mercury lamp as the light source. This 750 watt lamp was placed axially in a 50 liter capacity reactor 6.
  • the gas mixture prepared in 4 contained for one mole of methane, 6.25 moles of sulfur dioxide, 0.83 mole of chlorine and 0.417 mole of hydrogen chloride. This gas mixture was fed to the reactor at a rate of 5.75 Nm 3 / hour. The pressure in the reactor being fixed at 9 bars above the atmosphere, the temperature was adjusted to 65 ⁇ 2 ° C by injection, by means of the ramp 7, of 5.1 kg / h of liquid SO 2 .
  • the gaseous effluent, arriving by 14 in the second separator 15 had the following volume composition: Constituent % volume SO 2 83.06 CH 4 4.33 HCl 11.1 Cl 2 1.0 CH 3 Cl 0.5
  • this gaseous effluent was 6.57 Nm 3 / h and contained the gaseous SO 2 resulting from the evaporation which served to cool the reaction.
  • the temperature in the separator 15 was kept below 32 ° C.
  • the methane flow rate at the outlet 21 of the separator 15 was 0.278 Nm 3 / hour.
  • the quantity introduced in 1 being 0.68 Nm 3 / h, the conversion of methane was therefore 59%.
  • the hourly flow rate of the feed gas mixture had to be brought to 6.86 Nm 3 / hour.
  • the pressure in the reactor being fixed at 9 bars above the atmosphere, the temperature was adjusted to 65 ⁇ 2 ° C by injection, by means of the ramp 7, of 7.5 kg / h of sulfur dioxide liquid.
  • the gaseous effluent, arriving by 14 in the second separator 15 had the following volume composition: Constituent % volume SO 2 84.6 CH 4 3.17 HCl 10.81 Cl 2 0.92 CH 3 Cl 0.5
  • the methane flow rate at outlet 21 of separator 15 was 0.26 Nm 3 / hour.
  • the quantity introduced in 1 being 0.8 Nm 3 / h, the conversion of methane was therefore 67%.
  • the chloride productivity methanesulfonyl was 3.58 kg / kW.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP99400724A 1998-04-21 1999-03-25 Procédé de sulfochloration photochimique d'alcanes gazeux Expired - Lifetime EP0952147B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9804961 1998-04-21
FR9804961A FR2777565B1 (fr) 1998-04-21 1998-04-21 Procede de sulfochloration photochimique d'alcanes gazeux

Publications (2)

Publication Number Publication Date
EP0952147A1 EP0952147A1 (fr) 1999-10-27
EP0952147B1 true EP0952147B1 (fr) 2001-08-29

Family

ID=9525477

Family Applications (1)

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EP99400724A Expired - Lifetime EP0952147B1 (fr) 1998-04-21 1999-03-25 Procédé de sulfochloration photochimique d'alcanes gazeux

Country Status (8)

Country Link
US (1) US6045664A (zh)
EP (1) EP0952147B1 (zh)
JP (1) JPH11322703A (zh)
KR (1) KR19990083343A (zh)
CN (1) CN1149189C (zh)
CA (1) CA2267609A1 (zh)
DE (1) DE69900238T2 (zh)
FR (1) FR2777565B1 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2817258B1 (fr) * 2000-11-27 2003-01-10 Atofina Procede de sulfochloration photochimique d'alcanes gazeux
EP2459523A2 (en) * 2009-07-30 2012-06-06 Dow Global Technologies LLC Improved process for the sulfochlorination of hydrocarbons
US8916734B2 (en) 2010-10-21 2014-12-23 Sheeta Global Tech Corp. Using methanesulfonyl halide as a key intermediate for methane gas to liquid conversion and raw commodity chemical generation
WO2019144049A1 (en) * 2018-01-18 2019-07-25 Sheeta Global Tech Corp. Method of converting alkanes to alcohols, olefins and aromatics

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DEP20023B (de) * 1951-06-07 Imhausen & Co Gmbh Verfahren zur Sulfochlorisierung von flüssigen, gesättigten Kohlenwasserstoffen
US2352097A (en) * 1937-09-02 1944-06-20 Gen Aniline & Film Corp Production of organic compounds containing sulphur, chlorine, and oxygen
US2428733A (en) * 1938-05-13 1947-10-07 Gen Aniline & Film Corp Process for the preparation of organic sulfonyl chlorides
US2193824A (en) * 1938-06-30 1940-03-19 Du Pont Countercurrent reaction of hydrocarbons with sulphur dioxide and chlorine
US2174508A (en) * 1938-06-30 1939-09-26 Du Pont Process of reacting iso-alkanes with sulphur dioxide and chlorine and products thereof
US2335259A (en) * 1940-05-21 1943-11-30 Du Pont Process for the production of acid halides
US2462730A (en) * 1944-08-23 1949-02-22 Du Pont Preparation of polysulfonyl chlorides
US2709155A (en) * 1952-11-12 1955-05-24 Exxon Research Engineering Co Photochemical sulfo-chlorination
US2665305A (en) * 1952-11-20 1954-01-05 Standard Oil Dev Co Treatment of sulfonyl chlorides
US3238255A (en) * 1962-10-01 1966-03-01 Phillips Petroleum Co Aliphatic sulphonyl halides
DE1192191B (zh) * 1963-08-08
FR2246520B1 (zh) * 1973-10-04 1976-06-18 Aquitaine Petrole
DE2805441A1 (de) * 1978-02-09 1979-08-23 Basf Ag Verfahren zur herstellung von durch chloratome und/oder sulfochloridgruppen substituierten alkanen
JPS61158956A (ja) * 1984-12-29 1986-07-18 Toyo Kasei Kogyo Kk 塩化メタンスルホニルの製造方法
DE194931T1 (de) * 1985-03-14 1987-02-26 Societe Nationale Elf Aquitaine (Production), Courbevoie Verfahren und vorrichtung zur photochemischen sulfochlorinierung von gasfoermigen alkanen.
FR2578841B1 (fr) * 1985-03-14 1987-05-29 Elf Aquitaine Procede et appareil pour la sulfochloration photochimique d'alcanes gazeux
FR2595095B2 (fr) * 1986-03-03 1988-05-27 Elf Aquitaine Procede et appareil pour la sulfochloration photochimique d'alcanes gazeux
DE3708784A1 (de) * 1987-03-18 1988-09-29 Hoechst Ag Verfahren zur erhoehung der ausbeute bei durch licht initiierten reaktionen unter verwendung von gasentladungstrahlern

Also Published As

Publication number Publication date
CN1149189C (zh) 2004-05-12
CN1235155A (zh) 1999-11-17
EP0952147A1 (fr) 1999-10-27
DE69900238T2 (de) 2002-06-13
US6045664A (en) 2000-04-04
FR2777565A1 (fr) 1999-10-22
KR19990083343A (ko) 1999-11-25
FR2777565B1 (fr) 2000-05-19
CA2267609A1 (fr) 1999-10-21
JPH11322703A (ja) 1999-11-24
DE69900238D1 (de) 2001-10-04

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